Accelerators for two step adhesive systems

ABSTRACT

Benzoylthiourea or benzoylthiourethane derivatives as cure accelerators in primers for two step adhesive systems are provided.

BACKGROUND

1. Field

Benzoylthiourea or benzoylthiourethane derivatives as cure acceleratorsin primers for two step adhesive systems are provided.

2. Brief Description of Related Technology

Curable adhesive and sealant compositions oftentimes rely on curativesto make them commercially attractive options for end users. Curableadhesive and sealant compositions come in one part formats, two partformats and two step formats depending on the performance profile theyare designed to meet and the constituents used to prepare thecompositions. Anaerobic adhesives are prominent one part compositionsand generally are well-known. See e.g., R. D. Rich, “AnaerobicAdhesives” in Handbook of Adhesive Technology, 29, 467-79, A. Pizzi andK. L. Mittal, eds., Marcel Dekker, Inc., New York (1994), and referencescited therein. Their uses are legion and new applications continue to bedeveloped.

Conventional anaerobic adhesives ordinarily include a free-radicallypolymerizable acrylate ester monomer, together with a peroxy initiatorand an inhibitor component. Oftentimes, such anaerobic adhesivecompositions also contain accelerator components to increase the speedwith which the composition cures.

Anaerobic cure-inducing compositions ordinarily used in commercialanaerobic adhesive and sealant compositions to induce and acceleratecure ordinarily include saccharin, toluidines, such asN,N-diethyl-p-toluidine (“DE-p-T”) and N,N-dimethyl-o-toluidine(“DM-o-T”), acetyl phenylhydrazine (“APH”), maleic acid, and quinones,such as napthaquinone and anthraquinone. See e.g. U.S. Pat. Nos.3,218,305 (Krieble), 4,180,640 (Melody), 4,287,330 (Rich) and 4,321,349(Rich).

GC Corporation submitted to the U.S. Patent and Trademark Office apatent application, which published as U.S. Patent ApplicationPublication No. 2010/0249266, and is directed to a polymerizablecomposition comprising a first paste and a second paste, where the firstpaste comprises a polymer of α,β unsaturated monocarboxylic acid or α,βunsaturated dicarboxylic acid, water, and a hydroperoxide as a peroxide,and where the second paste comprises a (meth)acrylate compound nothaving an acid group, fluoroaluminosilicate glass powder, a thioureaderivative as a reducing material, and a vanadium compound as apolymerization accelerator.

Notwithstanding the state of the technology, there is an on-going desireto find alternative technologies for accelerating the cure of curablecompositions to differentiate existing products and provide supplyassurances in the event of shortages or cessation of supply of rawmaterials. Accordingly, it would be desirable to identify new materials,which function as accelerators for curable compositions.

SUMMARY

Benzoylthiourea or benzoylthiourethane derivatives for use asaccelerators in primers for two step adhesive systems are provided.

For instance, the benzoylthiourea or benzoylthiourethane derivatives maybe within general structure I

where Z is O or N—R, where R is selected from hydrogen, alkyl, alkenyl,hydroxyalkyl, hydroxyalkenyl, carbonyl, alkylene (meth)acrylate,carboxyl, or sulfonato, or R′ is a direct bond attaching to the phenylring; R′ is selected from hydrogen, alkyl, alkenyl, cycloalkyl, aryl,hydroxyalkyl, hydroxyalkenyl, alkylene- or alkenylene-ether, carbonyl,alkylene (meth)acrylate, carboxyl, nitroso or sulfonato; X is halogen,alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, carboxyl,nitroso, sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—,—NH—, and —PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2.

A more specific general structure is shown below:

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2.

More specifically, the benzoylthiourea or benzoylthiourethanederivatives may be within structures II or IIA, respectively

where R, R′, Z, X, Y, and n are as defined above.

More specific examples of the benzoylthiourea or benzoylthiourethanederivatives within structures II and IIA, respectively, are set forthbelow

where R, X, Y, and n are as defined above, and X′ is defined as X.

Alternatively, the benzoylthiourea or benzoylthiourethane derivativeswithin structure I may be a bis version, where R′ is a linker. That is,

where R, R′, X, Y, and n are as defined above, and m is 2.

The benzoylthiourea or benzoylthiourethane derivatives act to acceleratecure of curable compositions and provide adhesive systems with good curethrough volume. The present invention will be more fully appreciated bya reading of the “Detailed Description”, and the illustrative exampleswhich follow thereafter.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a rheometry plot of complex shear modulus versus time ina two step adhesive system comparing benzoylthiourea as a primer withLOCTITE 7649.

FIG. 2 depicts an exploded perspective view of a cut away of a liquidcrystal display device, illustrating three separate application layersof a LOCA between one or more of glass or PET, an ITO electrode, and anLCD panel.

FIG. 3 depicts a plot of CHP concentration (as weight percent in a LOCA)versus cure time (in minutes) for various BTU derivatives as a primer.

FIG. 4 depicts a plot of cure time (in minutes) versus CHP concentration(as weight percent in a LOCA) for BOTU as a primer.

FIG. 5 depicts a plot of LOCA thickness (in mils) versus cure time (inminutes) for each of 2% and 3% CHP additions to the LOCA using BMTU as aprimer.

DETAILED DESCRIPTION

Here, a primer uses cure accelerators within structure I

where Z is O or N—R, where R is selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2.

As noted above, a more specific general structure is shown below:

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2.

More specifically, the inventive cure accelerators may be withinstructures II and IIA respectively

where R, R′, X, Y, and n are as defined above.

More specific example of the inventive cure accelerators withinstructures II and IIA are set forth below

where R, X, Y, and n are as defined above, and X′ is defined as X.

And even more specifically, the inventive cure accelerators include

These benzoylthiourea or benzoylthiourethane derivatives may be used asan accelerator in a primer (in a solution, suspension or dispersion,together with an appropriate delivery vehicle or carrier) in two stepadhesive systems, where the benzoylthiourea or benzoylthiourethanederivatives are applied first onto a portion of substrate to be bondedfollowed by the anaerobically curable composition or applied after thecomposition has been applied. The benzoylthiourea or benzoylthiourethanederivatives display good solubility, stability and/or activity as cureaccelerators in curable compositions and as primers in an appropriatedelivery vehicle or carrier.

The invention provides a process for preparing a reaction product from acurable composition, comprising the steps of:

-   -   applying a compound within structures I or IA

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2, or

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2, to a desired substrate surface,

-   -   applying a composition comprising a (meth)acrylate component and        an oxidant to that desired substrate surface,    -   mating a second surface to that substrate surface to form an        assembly, and    -   exposing the assembly to appropriate conditions for a time        sufficient to cure the composition.

In yet another aspect, the invention provides a process for preparing areaction product from a curable composition, comprising the steps of:

-   -   applying a composition comprising a (meth)acrylate component and        an oxidant to a desired substrate surface,    -   applying a compound within structures I or IA

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2, or

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2, to that desired substrate surface,

-   -   mating a second surface to that substrate surface to form an        assembly, and    -   exposing the assembly to appropriate conditions for a time        sufficient to cure the composition.

In yet another aspect, the invention provides a process for preparing areaction product from a curable composition, comprising the steps of:

-   -   applying an oxidant to a desired substrate surface,    -   applying a composition comprising a (meth)acrylate component and        a compound within structures I or IA

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2, or

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2 to that desired substrate surface,

-   -   mating a second surface to that substrate surface to form an        assembly, and    -   exposing the assembly to appropriate conditions for a time        sufficient to cure the composition.

In yet another aspect, the invention provides a process for preparing areaction product from a curable composition, comprising the steps of:

-   -   applying a composition comprising a (meth)acrylate component and        a compound within structures I or IA

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2, or

where R and R′ are independently selected from hydrogen, alkyl, alkenyl,aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate, carbonyl,carboxyl, or sulfonato, or R and R′ taken together form a carbocyclic orhetero atom-containing ring, or R′ is a direct bond attaching to thephenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl,hydroxyalkenyl, alkoxy, amino, alkylene- or alkenylene-ether, alkylene(meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl orhaloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and —PO(NHCONHCSNH₂)NH—; andn is 0 or 1 and m is 1 or 2, to a desired substrate surface,

-   -   applying an oxidant to that desired substrate surface,    -   mating a second surface to that substrate surface to form an        assembly, and    -   exposing the assembly to appropriate conditions for a time        sufficient to cure the composition.

(Meth)acrylate monomers suitable for use as the (meth)acrylate componentin the two step adhesive systems may be chosen from a wide variety ofmaterials, such as these represented by H₂C═CGCO₂R¹, where G may behydrogen or alkyl groups having from 1 to about 4 carbon atoms, and R¹may be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl,aralkyl or aryl groups having from 1 to about 16 carbon atoms, any ofwhich may be optionally substituted or interrupted as the case may bewith silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester,carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur,sulfonate, sulfone and the like.

Additional (meth)acrylate monomers suitable for use herein includepolyfunctional (meth)acrylate monomers, such as, but not limited to,di-or tri-functional (meth)acrylates like polyethylene glycoldi(meth)acrylates, tetrahydrofuran (meth)acrylates anddi(meth)acrylates, hydroxypropyl (meth)acrylate (“HPMA”), hexanedioldi(meth)acrylate, trimethylol propane tri(meth)acrylate (“TMPTMA”),diethylene glycol dimethacrylate, triethylene glycol dimethacrylate(“TRIEGMA”), tetraethylene glycol dimethacrylate, dipropylene glycoldimethacrylate, di-(pentamethylene glycol) dimethacrylate, tetraethylenediglycol diacrylate, diglycerol tetramethacrylate, tetramethylenedimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate,trimethylol propane triacrylate and bisphenol-A mono anddi(meth)acrylates, such as ethoxylated bisphenol-A (meth)acrylate(“EBIPMA”), and bisphenol-F mono and di(meth)acrylates, such asethoxylated bisphenol-F (meth)acrylate.

Still other (meth)acrylate monomers that may be used herein includesilicone (meth)acrylate moieties (“SiMA”), such as those taught by andclaimed in U.S. Pat. No. 5,605,999 (Chu), the disclosure of which ishereby expressly incorporated herein by reference.

Of course, combinations of these (meth)acrylate monomers may also beused.

The (meth)acrylate component should comprise from about 10 to about 90percent by weight, such as about 60 to about 90 percent by weight, basedon the total weight of the adhesive system (exclusive of the carriervehicle, if the carrier vehicle evaporates prior to assembly and/orcure).

Additional components may be included in traditional curablecompositions to alter the physical properties of either the curablecompositions or the reaction products thereof.

For instance, one or more of maleimide components, thermalresistance-conferring coreactants, diluent components reactive atelevated temperature conditions, mono- or poly-hydroxyalkanes, polymericplasticizers, and chelators (see U.S. Pat. No. 6,043,327, the disclosureof which is hereby expressly incorporated herein by reference) may beincluded to modify the physical property and/or cure profile of theformulation and/or the strength or temperature resistance of the curedadhesive.

When used, the maleimide, coreactant, reactive diluent, plasticizer,and/or mono- or poly-hydroxyalkanes, may be present in an amount withinthe range of about 1 percent to about 30 percent by weight, based on thetotal weight of the composition.

The curable compositions may also include other conventional components,such as free radical initiators, other free radical co-accelerators,inhibitors of free radical generation, as well as metal catalysts, suchas iron and copper. Depending on the cure environment some or all ofthese components might ordinarily be used, particularly if cure is tooccur under anaerobic conditions.

A number of well-known initiators of free radical polymerization (or,oxidants) are typically incorporated into the curable compositionsincluding, without limitation, hydroperoxides, such as cumenehydroperoxide (“CHP”), para-menthane hydroperoxide, t-amylhydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and t-butylhydroperoxide (“TBH”). Other peroxides include t-butyl perbenzoate,benzoyl peroxide, dibenzoyl peroxide,1,3-bis(t-butylperoxyisopropyl)benzene, diacetyl peroxide, butyl4,4-bis(t-butylperoxy)valerate, p-chlorobenzoyl peroxide, cumenehydroperoxide, t-butyl cumyl peroxide, t-butyl perbenzoate, di-t-butylperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane,2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-yne,4-methyl-2,2-di-t-butylperoxypentane and combinations thereof.

It may be desirable in some instances, to provide the oxidant in anencapsulated form.

Such oxidants are typically employed in the range of from about 0.1 toabout 10 percent by weight, based on the total weight of thecomposition, with about 1 to about 5 percent by weight being desirable.

Stabilizers and inhibitors (such as phenols including hydroquinone andquinones) may also be employed to control and prevent premature oxidantdecomposition and polymerization of the curable compositions.

In the context of anaerobic curable compositions, chelating agents [suchas the tetrasodium salt of ethylenediamine tetraacetic acid (“EDTA”)] totrap trace amounts of metal contaminants therefrom, may also be used.When used, chelators may ordinarily be present in the compositions in anamount from about 0.001 percent by weight to about 0.1 percent byweight, based on the total weight of the composition.

The benzoylthiourea or benzoylthiourethane derivatives may be used ascure accelerators in amounts of about 0.1 to about 5 percent by weight,such as about 1 to about 2 percent by weight, based on the total weightof the composition.

Other agents such as thickeners, non-reactive plasticizers, fillers,toughening components (such as elastomers and rubbers), and otherwell-known additives may be incorporated therein where the art-skilledbelieves it would be desirable to do so.

The adhesive system may be prepared using conventional methods which arewell known to those persons of skill in the art. For instance, thecomponents of the curable composition may be mixed together in anyconvenient order consistent with the roles and functions the componentsare to perform in the compositions. Conventional mixing techniques usingknown apparatus may be employed.

The two step adhesive system may be used to bond a variety of substratesto perform with the desired benefits and advantages described herein.For instance, appropriate substrates may be constructed from steel,brass, copper, aluminum, zinc, glass and other metals and alloys,ceramics and thermosets.

The so-described benzoylthiourea or benzoylthiourethane derivatives maybe used in two-step adhesive systems, where exposure to radiation in theelectromagnetic spectrum may be used to initiate cure, with curecontinuing in those regions of the bond line that are not accessible (orhave limited access) to such radiation, such as where opaque substratesare to be bonded. This is known as shadow curing.

Because conventional photocurable adhesive compositions undergophotoinitiated polymerization in those regions of the bond line thathave been subjected to radiation in the electromagnetic spectrum but notin other regions, a secondary cure mechanism to affect polymerization inthe unirradiated areas, such as may be found in the interior of the bondline, is often used, particularly when opaque substrates are to bebonded as noted above.

One such secondary cure mechanism used in the past relies upon theaddition to the compositions of heat-activated peroxides. However,heat-activated peroxides ordinarily use temperatures in excess of 100°C. to initiate polymerization, which is undesirable particularly whenheat-sensitive, components are involved. Isocyanates, which are moisturereactive, have been used in the past to provide such a secondary cure.Health and environmental concerns over the use of isocyanates havelimited their acceptance. Moisture curable silicones have also been usedto impart shadow cure properties to warble compositions. Long cureperiods required to build the adhesive strength make them a lessappealing approach.

In the context of two-step adhesive systems, here, instead of theconventional approaches, a primer of the so-described benzoylthiourea orbenzoylthiourethane derivatives may be used to cure the adhesivecomposition through the bond line. The primer is applied as a solution,dispersion or emulsion of the benzoylthiourea or benzoylthiourethanederivative in a suitable carrier. Or, where the benzoylthiourea orbenzoylthiourethane derivative is itself a liquid, it may be appliedneat.

In one such application of the benzoylthiourea or benzoylthiourethanederivative as a primer with a liquid optically clear adhesive (“LOCA”)composition, the primer is applied to at least a peripheral portion ofthe underside of the touch panel of a hand held display device, whichwhen assembled will not have appreciable visibility to a light sourceused to cure the adhesive with which the accelerator is to be used.Reference to FIG. 2 shows an exploded perspective view of theconstruction of a liquid crystal display module. Such a module may beused to fabricate television sets, computer monitors, computer tabletsand mobile phones, for instance. In the module shown in FIG. 2, threeinstances of LOCA composition placement may be found: one between aliquid crystal display panel and a glass substrate; one between a glasssubstrate (the same glass substrate referred to above) and an indium tinoxide-coated electrode; and one between a glass or polyethyleneterephthalate substrate and an ITO-coated electrode (the same ITO-coatedelectrode referred to above).

In view of the above description, it is clear that a wide range ofpractical opportunities is provided. The following examples are providedfor illustrative purposes only, and are not to be construed so as tolimit in any way the teaching herein.

EXAMPLES

Many of so-described benzoylthiourea or benzoylthiourethane derivativeswere synthesized as set forth below.

A. Syntheses Benzoyl Isothiocyanate

Benzoyl isothiocyanate was prepared as a starting material for benzoylthiourea and derivates thereof. In a 500 mL three-neck round-bottomflask (“RBF”), fitted with a condenser, thermo-probe, sealed systemnitrogen purge, pressure-equilibrated addition funnel and mechanicalstirrer, were placed solid ammonium thiocyanate (16.9 g, 0.22 mol) anddichloromethane (100 mL). The stirred mixture was cooled in an ice-waterbath to a temperature of about 10-15° C. To the stirred mixture wasadded a solution of benzoyl chloride (28.4 g, 0.2 mol) indichloromethane (50 mL) over a period of time of 20 minutes and thereaction mixture was warmed to a temperature near reflux (39° C.) for aperiod of time of 1 hour. Reaction completion was confirmed by FT-IRanalysis. The solution was then cooled to a temperature of about 10-15°C. The solution can be concentrated to an oil to provide the benzoylisothiocyanate. A boiling point of 128-131° C. at 15 mm Hg was measured.

FT-IR, ATR-Accessory, 3063 cm⁻¹ (aromatic C—H), 2000-1921 (—NCS aromaticisothiocyanate), 1685 (carbonyl), 1230 (—C—N—), 846 (aromaticthioisocyanate).

¹H—NMR DMSOd₆, δ 8.05 (s, multiplet, aromatic H), 7.70 (s, triplet,aromatic H), 7.50 (s, triplet, aromatic H).

¹³C NMR—DMSOd₆, δ 161.0 (s, singlet, Ar—CO—), 148.0 (s, singlet, —NCS),135.0 (m, singlet, aromatic C), 130.0 (s, singlet, aromatic C), 128.0(s, singlet, aromatic C).

Benzoylthiourea

The RBF was changed to include a sealed glass-fritted bubbler systemconnected to an ammonia gas supply and an exit bubbler-scrubber system.To the clear cold reaction mixture (controlled at a temperature below30° C. with an external ice-water bath) was slowly purged ammonia gas.During the addition, ammonia was consumed and the reaction mixtureslowly became pale and cloudy/milky in appearance. The mixture wasallowed to warm to room temperature, and stirring continued for anadditional hour after ammonia addition ceases. Nitrogen gas was thenre-introduced into the system to purge residual ammonia gas. Theresulting solid is collected by vacuum filtration and washed withadditional dichloromethane to provide a slightly yellow solid, which wasrecrystallized from ethanol. The solid was then dried to a constantweight in vacuo at a temperature of 50° C. and a pressure of <1 mTorr.The resulting solid was observed to have a melting point of 171.62° C.,as determined by DSC.

FT-IR, ATR-Accessory, 3301-3146 cm⁻¹ (—NH₂ and —NH—), 1675 (carbonyl),1599, 1526 and 1403 (—NCSN—), 1233 (—C—N—).

¹H NMR—DMSOd₆, δ 11.1 ppm (m, singlet, —NH—), 9.90 and 9.55 doublet,—NH₂), 7.90 (s, doublet, aromatic H), 7.60-7.40 (s, multiplet, aromaticH), 3.65 (s, singlet, solvent exchange).

¹³C NMR—DMSOd₆, δ 187.5 ppm (NH—CS—NH₂), 173.5 (Ar—CO—), 139.0-132.0(aromatic C).

Benzoyl Thiourea Adducts Made from Amine- or Nitrogen-ContainingCompounds

Benzoyl Morpholine Thiourea (“BMTU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point morpholine (13.21 g, 0.150mol) and dichloromethane (100 mL) were added slowly over a period oftime of about 30 minutes. The ice-water bath was removed and thereaction mixture was stirred overnight under a nitrogen purge. Thereaction mixture was then concentrated in vacuo at a temperature of 40°C. to provide a crude yellow solid. The solid was recrystallized fromrefluxing ethyl acetate (50 mL) to provide a yellow solid that was driedto constant weight in vacuo at a temperature of 50° C. and a pressure of<1 mTorr in a 82% yield. The solid was determined to have a meltingpoint of 138° C.

Benzoyl Octyl Thiourea (“BOTU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath toa temperature of below 5° C., at which point octylamine (19.6 g, 0.150mol) and dichloromethane (100 mL) was added slowly over a period of timeof 30 minutes. The ice-water bath was removed and the reaction mixturewas stirred at room temperature under a nitrogen purge overnight. Thereaction mixture was washed with water, and the organic layer separated,dried with anhydrous magnesium sulfate, filtered and concentrated invacuo at a temperature of 40° C. to provide an orange oil. The oil wasdried to constant weight in vacuo at a temperature of 50° C. and apresence of <1 mTorr in a 95% yield.

Benzoyl Thiodiethylurea (“BTDEU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point diethylamine (15.0 g, 0.150mol) and dichloromethane (100 mL) were added slowly over a period oftime of about 30 minutes. The ice-water bath was removed and thereaction mixture was stirred under a nitrogen purge overnight. Thereaction mixture was then concentrated in vacuo at a temperature of 40°C. to provide an orange-yellow solid. The solid was dried to constantweight in vacuo at a temperature of 50° C. and a pressure of <1 mTorr ina 99% yield.

Benzoyl Thiodihydroxyethylurea (“BTDHEU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point dihydroxyethylamine (15.9 g,0.150 mol) and dichloromethane (100 mL) were added slowly over a periodof time of about 30 minutes. The ice-water bath was removed and thereaction mixture was stirred under a nitrogen purge overnight. Thereaction mixture was then concentrated in vacuo at a temperature of 40°C. to provide a white solid. The solid was dried to constant weight invacuo at a temperature of 50° C. and a pressure of <1 mTorr in a 97%yield.

Benzoyl Tetrahydroquinoline Thiourea (“BTHQTU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point tetrahydroquinoline (20.4 g,0.150 mol) and dichloromethane (100 mL) were added slowly over a periodof time of about 30 minutes. The ice-water bath was removed and thereaction mixture was stirred under a nitrogen purge overnight. Thereaction mixture was then concentrated in vacuo at a temperature of 40°C. to provide a white solid. The solid was dried to constant weight invacuo at a temperature of 50° C. and a pressure of <1 mTorr in a 93%yield. The solid was determined to have a melting point of 143.6° C.

Benzoyl Cyclohexythiourea (“BCHTU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point cyclohexylamine (15.0 g, 0.150mol) and dichloromethane (100 mL) were added slowly over a period oftime of about 30 minutes. The ice-water bath was removed and thereaction mixture was stirred under a nitrogen purge overnight. Thereaction mixture was then concentrated in vacuo at a temperature of 40°C. to provide an orange-yellow solid. The solid was dried to constantweight in vacuo at a temperature of 50° C. and a pressure of <1 mTorr ina 99% yield. The solid was determined to have a melting point of 67.8°C.

Cyclohexyl Bis-Benzoylthiourea (“CHbisBTU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point benzoyl isothiocyanate (50.0g, 0.300 mol) and cyclohexyldiamine (17.42 g, 0.150 mol) anddichloromethane (100 mL) were added slowly over a period of time ofabout 30 minutes. The ice-water bath was removed and the reactionmixture was stirred under a nitrogen purge overnight. The reactionmixture was then concentrated in vacuo at a temperature of 40° C. toprovide an orange-yellow solid. The solid was dried to constant weightin vacuo at a temperature of 50° C. and a pressure of <1 mTorr in a 99%yield.

Benzoyl Naphthosultamthiourea (“BNSTU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point naphthosultam (31.4 g, 0.150mol) and dichloromethane (100 mL) were added slowly over a period oftime of about 30 minutes. The ice-water bath was removed and thereaction mixture was stirred under a nitrogen purge overnight. Thereaction mixture was then concentrated in vacuo at a temperature of 40°C. to provide a brown solid. The brown solid was recrystallized fromrefluxing ethyl acetate (150 mL) to provide a tan solid that was driedto constant weight in vacuo at a temperature of 50° C. and a pressure of<1 mTorr in a 77% yield. The resulting solid was observed to have amelting point of 264° C.

Benzoyl Phenylhydrazinethiourea (“BPHTU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point phenylhydrazine (16.7 g, 0.150mol) and dichloromethane (100 mL) were added slowly over a period oftime of about 30 minutes. The ice-water bath was removed and thereaction mixture was stirred under a nitrogen purge overnight. Thereaction mixture was then concentrated in vacuo at a temperature of 40°C. to provide a white solid. The solid was dried to constant weight invacuo at a temperature of 50° C. and a pressure of <1 mTorr in a 97%yield.

Benzoyl Thiourea Propyltrimethoxysilane (“BTU-TMS”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The reaction mixture was cooled in anice-water bath to a temperature below 5° C., at which point3-aminopropyl trimethoxysilane (27.7 g, 0.150 mol) and dichloromethane(100 mL) were added slowly over a period of time of 30 minutes. Theice-water bath was removed and the reaction mixture was stirred at roomtemperature under a nitrogen purge overnight. The reaction mixture wasthen concentrated in vacuo at a temperature of 40° C. to provide a clearred liquid. The liquid was dried to constant weight in vacuo at atemperature of 50° C. and a pressure of <1 mTorr in a 97% yield.

Benzoyl Thiourea JEFFAMINE (“BTU-JEFFAMINE”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The reaction mixture was cooled in anice-water bath to a temperature below 5° C., at which point JEFFAMINEED-900 (67.5 g, 0.075 mol) and dichloromethane (100 mL) was added slowlyover a period of time of 30 minutes. JEFFAMINE ED-900, according to themanufacturer Huntsman Corporation, Woodlands, Tex., is a polyetherdiamine based on a predominantly PEG backbone, with a molecular weightof 900. In the structure given above, 1 is about 12.5, and m+n is about6.

The ice-water bath was removed and the reaction mixture was stirred atroom temperature under a nitrogen purge overnight. The cloudy solutionwas then concentrated in vacuo at a temperature of 40° C. to provide apale amber oil. The liquid was dried to constant weight in vacuo at atemperature of 50° C. and a pressure of <1 mTorr in a 99% yield.

Benzoyl Saccharin Thiourea (“BSTU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) and saccharin (28.1g, 0.150 mol) followed by dichloromethane (100 mL). The mixture wascooled in an ice-water bath at a temperature below 5° C., at which pointwater (28.1 g, 0.150 mol) and acetone as the solvent and dichloromethane(100 mL) were added slowly over a period of time of about 30 minutes.The ice-water bath was removed and the reaction mixture was stirredunder a nitrogen purge overnight. The reaction mixture was thenconcentrated in vacuo at a temperature of 40° C. to provide a solid thatwas dried to constant weight in vacuo at a temperature of 50° C. and apressure of <1 mTorr in a 37% yield.

Benzoyl Diacetamide Thiourea (“BDTU”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point diacetamide (15.3 g, 0.150mol) and acetone as the solvent and dichloromethane (100 mL) were addedslowly over a period of time of about 30 minutes. The ice-water bath wasremoved and the reaction mixture was stirred under a nitrogen purgeovernight. The reaction mixture was then concentrated in vacuo at atemperature of 40° C. and then dried to constant weight in vacuo at atemperature of 50° C. and a pressure of <1 mTorr.

Para-Toluene Sulfonyl Thiourea (“pTSTU”) Adduct

In a 100 mL RBF equipped with a condenser, thermo-probe, sealed systemnitrogen purge, pressure-equilibrated addition funnel and magneticstirrer were placed thiourea (9.36 g, 0.12 mol) and dioxane (50 mL). Themixture was warmed to a temperature of 100° C. to encourage dissolution.The mixture was then cooled to a temperature of about 20° C., at whichpoint para-toluenesulfonylisocyanate (25.0 g, 0.12 mol) was added slowlyover a period of time of 1 hour. A milky-white suspension was observedto form. The temperature was maintained with an ice-water bath between20° C. and 32° C. The reaction mixture was stirred overnight at roomtemperature before it was concentrated in vacuo at a temperature of 40°C. to yield a white solid that was further dried to constant weight invacuo at a temperature of 50° C. and a pressure of <1 mTorr.

Benzoyl Dodecylthiourea (“BDDTU”) Adduct

In a 250 mL 3-neck RBF equipped with a condenser, thermo-probe, sealedsystem nitrogen purge, pressure-equilibrated addition funnel andmagnetic stirrer were placed benzoyl isothiocyanate (25.0 g, 0.150 mol)and ethyl acetate (100 mL). The mixture was cooled in an ice-water bathbelow 5° C., at which point melted dodecylamine (29.3 g, 0.150 mol)(m.p. 30° C.) and ethyl acetate (100 mL) was added slowly over a periodof time of 0.5 hours. The ice-water bath was removed and the cloudysolution was stirred at 40° C. under nitrogen purge overnight. Theorganic phase was separated, washed with water, dried over anhydrousmagnesium sulfate, filtered and concentrated in vacuo at a temperatureof 40° C. to yield a yellow powdery solid. The solid was dried toconstant weight in vacuo at 40° C. and <1 mTorr (99%).

Benzoyl Octadecylthiourea (BODTU) Adduct

In a 500 mL 3-neck RBF equipped with a condenser, thermo-probe, sealedsystem nitrogen purge, pressure-equilibrated addition funnel andmagnetic stirrer were placed benzoyl isothiocyanate (16.07 g, 96.5 mol)and ethyl acetate (50 mL). The mixture was cooled in an ice-water bathbelow 5° C., at which point melted octadecylamine (26.5 g, 96.5 mol)(m.p. 55° C.) and ethyl acetate (50 mL) was added slowly over a periodof time of 1 hour. The ice-water bath was removed and the cloudysolution was stirred at 50° C. under nitrogen purge overnight. Theorganic phase was separated, washed with water, dried over anhydrousmagnesium sulfate, filtered and concentrated in vacuo at a temperatureof 40° C. to yield a pale powdery (waxy) solid. The solid was dried toconstant weight in vacuo at 40° C. and <1 mTorr (99%).

Benzoyl Thiourea Adducts Made from Hydroxyl-Containing Compounds

Benzoyl Thiourea Hexanol (“BTU-H”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point hexanol (15.5 g, 0.150 mol)and acetone (as the solvent) were added slowly over a period of time ofabout 30 minutes. The ice-water bath was removed and the reactionmixture was stirred under a nitrogen purge overnight. The reactionmixture was then concentrated in vacuo at a temperature of 40° C. toprovide a yellow solid. The solid was dried to constant weight in vacuoat a temperature of 50° C. and a pressure of <1 mTorr in a 83% yield.

Benzoyl Thiourea Hydroxyethyl Methacrylate (“BTU-HEMA”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point hydroxyethyl methacrylate(19.5 g, 0.150 mol) and acetone (as the solvent) were added slowly overa period of time of about 30 minutes. The ice-water bath was removed andthe reaction mixture was stirred under a nitrogen purge overnight. Thereaction mixture was then concentrated in vacuo at a temperature of 40°C. to provide a pale yellow solid. The solid was dried to constantweight in vacuo at a temperature of 50° C. and a pressure of <1 mTorr ina yield of 77%.

Benzoyl Thiourea Water (“BTU-W”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point water (2.7 g, 0.150 mol) andacetone (as the solvent) were added slowly over a period of time ofabout 30 minutes. The ice-water bath was removed and the reactionmixture was stirred under a nitrogen purge overnight. The reactionmixture was then concentrated in vacuo at a temperature of 40° C. toprovide a pale yellow solid. The solid was dried to constant weight invacuo at a temperature of 50° C. and a pressure of <1 mTorr in a 36%yield.

Benzoyl Thiourea Cyclohexyl (“BTU-CH”) Adduct

To a 250 mL 3-neck RBF equipped with a condenser, magnetic stirrer,thermo-probe, nitrogen purge and pressure-equilibrated addition funnelwas added benzoyl isothiocyanate (25.0 g, 0.150 mol) followed bydichloromethane (100 mL). The mixture was cooled in an ice-water bath ata temperature below 5° C., at which point cyclohexanol (15.2 g, 0.150mol) and acetone (as the solvent) were added slowly over a period oftime of about 30 minutes. The ice-water bath was removed and thereaction mixture was stirred under a nitrogen purge overnight. Thereaction mixture was then concentrated in vacuo at a temperature of 40°C. and then was dried to constant weight in vacuo at a temperature of50° C. and a pressure of <1 mTorr.

B. Use as a Primer in Two Step Adhesive Systems

1. Comparison with LOCTITE 7649

Saccharin (0.5 g) and acetyl phenylhydrazine (0.5 g) were dissolved in2-hydroxyethyl methacrylate (7.3 g) and acrylic acid (2.45 g) to form asolution, which was added to urethane methacrylate resin (87.99 g). CHP(1 g) was also added to the composition to form the adhesive part of thetwo step system.

As a primer, BTU (1 g) was dissolved in acetone (99 g).

As a control, LOCTITE 7649 was used. LOCTITE 7649 consists of a coppersalt and an aliphatic amine in acetone.

Each primer was applied onto a pair of two aluminum plates in sufficientquantity to cover the inwardly facing surface of the plates; thistypically required about 3 drops for a 8 mm diameter plate. Each pair ofaluminum plates was then loaded onto a Physica MCR301 rheometer, and thegap between them was zeroed. As a primer-less control, the plates wereloaded and the gap zeroed without the application of any primer.

The top plate was withdrawn to a distance of 75 mm, and the adhesivepart was loaded onto the bottom plate. The top plate was then lowered tothe specified gap.

An oscillatory experiment was performed at a temperature of 25° C. with1% strain, 30 rad/s angular frequency, 0.55 mm initial gap, and normalforce fixed at 0 N. Results are shown in FIG. 1. The BTU primer provideda higher cured modulus and reached ultimate cure in less time thanLOCTITE 7649.

2. Comparison with PRIMER T

PRIMER T, commercially available from Henkel Corporation, Rocky Hill,Conn., contains:

Component Amt (wt %) Acetone 85.75 Isopropanol, anhydrous grade 12.252-Mercaptobenzothiozole 0.9 N,N-Diethanol-p-toluidine 1.1

The 2-mercaptobenzothiozole in PRIMER T was replaced at an equal weightwith each of tetramethyl thiourea and BTU, and evaluated compared withPRIMER T for its performance as a primer in a two step adhesive systemwith LOCTITE 2701.

The BTU-primed stainless steel substrates showed a fixture time of lessthan 1 hour across 500 micron gap stainless steel substrates. Thefixture time was reduced to about 20 minutes on mated GMBS substrateswith the same gap.

Stainless Steel Fixture Time (mins)/Gap Primer 0 250 μm 500 μm None 11to 20 >70 >145 PRIMER T 10 to 20 >80 Not tested Tetramethyl Thiourea 15to 25 >70 Not tested BTU <5 10 to 15  <60

GBMS Fixture Time (mins)/Gap Primer 0 250 μm 500 μm None 15 to30 >160 >180 PRIMER T 15 to 30 20 to 30  >67 Tetramethyl Thiourea <15110 to 140 Not tested BTU  <6 10 to 20 15 to 30

Tensile shear strength after curing for 24 hours also show the BTU to besuperior in gap cure in comparison to the other candidates, particularlyon stainless steel.

Stainless Shear Strength/Gap Primer 0 250 μm 500 μm None 9.24 2.08 0.10PRIMER T 5.99 1.92 0.44 Tetramethyl Thiourea 8.44 4.72 1.38 BTU 5.995.59 6.97

GBMS Shear Strength/Gap Primer 0 250 μm 500 μm None 16.75 9.03 3.27PRIMER T 18.69 13.65 9.13 Tetramethyl Thiourea 18.88 12.78 7.68 BTU18.16 14.36 9.46

A similar evaluation, as with LOCTITE 2701, was performed with each ofLOCTITE 5188, 326, and 270 on unprimed stainless steel substrates andones primed with BTU and PRIMER T. The BTU-primed substrates showed asignificant improvement in fixture time for 5188 and 326, as may be seenwith reference to the tables below.

BTU Fixture Time (mins)/Gap Product 0 250 μm 500 μm 5188 <5 <10 15-20326 2-3 5-10 11-30 270 <5 5-10 12-19

PRIMER T Fixture Time (minutes)/Gap Product 0 250 μm 500 μm 5188 21-49Not Tested* Not Tested* 326 30-60 270 35-60 *0 gap fixture time was tooslow to be practical

No Primer Fixture Time (mins)/Gap Product 0 250 μm 500 μm 5188 >60 NotTested Not Tested 326 5-6 >100 >100 270 13-30 >120 >120

LOCTITE 326 showed virtually no loss in strength from 0 to 500 microngap, whether after one hour room temperature cure or 24 hours roomtemperature cure.

1 Hour RTC Tensile Shear Strength (N/mm²) Product 0 Gap 250 μm 500 μm5188 7.17 6.90 2.94 326 11.81 13.28 10.16

24 Hour RTC Tensile Shear Strength (N/mm²) Product 0 Gap 250 μm 500 μm5188 7.69 6.87 5.35 326 12.76 15.29 12.11

BTU derivatives as primers were also evaluated. Here, compounds A-I wereevaluated as primers, as shown and described below.

Fixture times a Stainless steel substrates are reported below for BTUand compounds A-C:

Primer/Fixture Time (mins) Gap BTU A B C 0 5 60 10 5 250 μm  6-15Fixture 20 10 after 24 hours 500 μm 11-15 Some 60 15 failure of bondseven after 24 hours

Compound C shows useful benefits even over BTU itself at zero gap, butBTU itself performs much better through gap.

Fixture times on stainless steel substrates are reported below in thetable for compounds D-G. For compound E no fixture was observed in 60minutes at a gap of 250 μm or 500 μm.

Primer/Fixture time (mins) Gap D E F G 0 10 60 10 10 250 μm 20 Nofixture 25 25 500 μm </+50 No fixture 45 45

Fixture times on stainless steel substrates are reported below forcompounds H and I. For compound I no fixture was observed in 60 minutesat a gap of 250 μm or 500 μm.

Primer/Fixture Time (mins) Gap H I 0 10 60 250 μm 20 No fixture 500 μm40 No fixture

While some BTU derivatives match or even outperform BTU as a primer intwo step adhesive systems at zero gap and even at a gap of 250 microns,BTU itself still stands out at a gap of 500 microns.

The two-step adhesive system using the primer approach is particularlyattractive with liquid optically clear adhesive (“LOCA”) compositions.These LOCA compositions are attractive options for the assembly ofliquid crystal display modules. (See FIG. 2.)

C. Use as a Primer with LOCA Composition

LOCA compositions used here are available commercially from HenkelCorporation, Rocky Hill, Conn., under the trade names LOCTITE 3191,3192, 3193, 3195, and 3196. For instance, LOCTITE 3195 containspolymerizable (meth)acrylated rubber resins with a molecular weight ofup to 100,000 and IRGACURE 184 (commercially available from BASFCorporation) as a photoinitiator. A hydroperoxide-based oxidizing agent,here CHP, was added in varying amounts, up to 10% based on the(meth)acrylated rubber resins. The primer here was chosen from one ofBTU, BOTU, BCHTU, BTDEU, BMTU, JEFFAMINE BTU, p-TSI TU, and BPHTU andemployed as a 5% solution in an acetone/isopropanol solvent mixture. InFIG. 3, the effect of the CHP level on shadow cure profiles is shown forBMTU, BOTU, BCHTU and BTDEU as primers.

A primer of a pre-determined volume was applied onto a glass substrate(dimensions: 1″×4″) in an amount of about 0.3 ml and allowed to air dryfor about 10-15 minutes. A 2 mil thick layer of the LOCA composition wasthen applied on another glass slide. The primer coated glass substratewas brought into contact with a second glass substrate previously coatedwith the LOCA composition. The total contact area where the primer andthe LOCA composition layer are in contact is between 1″×2″. Eachsubstrate assembly was then allowed to cure for various pre-determinedtimes before being subjected to adhesion evaluation in shear mode with aknown weight (100 grams).

Each primer was applied to a glass slide in an amount of about 0.3 mland allowed to air dry for about 10-15 minutes. A 2 mil thick layer ofthe LOCA composition was then applied on another glass slide.

Primer No./Identity Cure 5 6 Time 2 3 4 JEFFAMINE p-TSI 7 8 9 (hours)BTU BMTU BPHTU BTU TU BOTU BCHTU BTDEU 0.5 Not Cured Not Not cured NotCured Cured cured cured cured cured 1 Not — Not Not cured Not — — —cured cured cured 1.5 Not — Not Not cured Not — — — cured cured cured 2Not — Not Not cured Not — — — cured cured cured 18 Not — Not Not curedNot — — — cured cured cured 24 Cured — Not Not cured Not — — — curedcured

BOTU was selected to demonstrate the primer efficacy at various usagelevels and various cure time periods. The primer usage level was variedby changing the concentration. As above, LOCTITE 3195 with 3% by weightcumene hydroperoxide was used as the LOCA composition at a 2 milthickness. The shadow cure results with various levels of BOTU primerare shown in the table below. More specifically, Sample Nos. 7-1 through7-6 used respectively 5.0%, 2.5%, 1.25%, 0.63%, 0.31% and 0.15%.

Cure Primer No. 7/Amt (wt %) Time 7-1 7-2 7-3 7-4 7-5 7-6 (mins) 5.0%2.50% 1.25% 0.63% 0.31% 0.15% 10 Cured Cured Cured Cured Partially Notcured cured 20 — — — — Cured Not cured 30 — — — — — Not cured 60 — — — —— Not cured 120 — — — — — Not cured

BMTU was selected to demonstrate primer effectiveness for shadow cure atvarious thicknesses of adhesive layer. BMTU was used as a 5% solution inan acetone/isopropanol solvent mixture. The LOCA composition used herewas as above. The adhesive thickness was varied from direct contact to10 mils and the cure time was varied too. The variables and results areshown below in the table.

LOCTITE 3195 CHP/Application Thickness (mil) Cure Time 3195-1 3195-23195-3 3195-4 3195-5 3195-6 (mins) ~0 2 4 6 8 10 10 Not Not Not Not NotNot cured cured cured cured cured cured 20 Not Not Not Not Not Not curedcured cured cured cured cured 30 Cured Not Not Not Not Not cured curedcured cured cured 40 — Not Not Not Not Not cured cured cured cured cured50 — Cured Not Not Not Not cured cured cured cured 60 — — Not Not NotNot cured cured cured cured 70 — — Not Not Not Not cured cured curedcured 80 — — Cured Not Not Not cured cured cured 90 — — — Cured Not Notcured cured 100 — — — — Cured Cured

BMTU was also used to establish a shadow cure profile with variouslevels of the cumene-hydroperoxide oxidizing agent in the LOCAcomposition. More specifically, Sample Nos. 3195-7 to 3195-11 hadrespectively 0%, 0.5%, 1%, 2% and 3% CHP. The base LOCA composition andthe primer concentration was used as before. The results are shown belowin the table.

Cure Time LOCTITE 3195/CHP (hours) 3195-7 3195-8 3195-9 3195-10 3195-111 Not cured Not cured Not cured Cured Cured 2 Not cured Not cured Cured— — 3 Not cured Not cured — — — 24 Not cured Cured — — —

Three BTU derivatives—BMTU, BOTU, and BCHTU—were used as a primer withcumene hydroperoxide-containing LOCA compositions. Each LOCA compositionwas applied to a glass substrate at a thickness of 2 mil. The tablebelow shows the shadow cure profiles of five noted LOCA compositionswith the three noted BTU primers.

Adhesive Identity/ Cure Time (min) Primer 3191-1 3191-2 3191-3 LOCTITE3191 BMTU BOTU BCHTU 10 Not cured Cured Cured 20 Not cured — — 30 Notcured — — 40 Not cured — — 50 Not cured — — 60 Cured — — 3192-1 3192-23193-3 LOCTITE 3192 BMTU BOTU BCHTU 10 Not cured Not Cured Cured 20 Notcured Not Cured — 30 Not cured Not Cured — 40 Not cured Cured — 50 Notcured — — 60 Not cured — — 3193-1 3193-2 3193-3 LOCTITE 3193 BMTU BOTUBCHTU 10 Not cured Not cured Cured 20 Not cured Cured 30 Not cured 40Not cured 50 Not cured 60 Not cured 3194-1 3194-2 3194-3 LOCTITE 3194BMTU BOTU BCHTU 10 Not cured Cured Cured 20 Not cured — — 30 Not cured —— 40 Cured — — 50 — — — 60 — — — 3195-1 3195-2 3195-3 LOCTITE 3195 BMTUBOTU BCHTU 10 Not cured Not cured Cured 20 Not cured Not cured — 30 Notcured Not cured — 40 Not cured Cured — 50 Not cured — — 60 Cured — —

Reference to FIGS. 4 and 5 also shows the benefits of certainbenzoylthiourea derivatives as primers together with oxidant-containingLOCA compositions on cure time and cure through volume, respectively.

Here, adhesive compositions based on (meth)acrylated silicones wereevaluated in a two-step adhesive system with BTU derivatives as primers.A series of SILMER-branded reactive silicones (available commerciallyfrom Siltech), were used to assess the effectiveness of the BTUderivatives as primers for the acrylate functional siliconepre-polymers.

Two materials—BOTU and BCHTU—were used to shadow cure the SILMER-brandedsilicone pre-polymers. In each example shown in the table below 0.3 mlof a 5% primer solution was employed and each adhesive compositioncontained 3% by weight of cumene hydroperoxide as an oxidizing agent.

SILMER/Fixture Time (mins) Primer Di-25* Di-50⁺ Di-1010^(✓) Di-1508^(x)Di-2510^(@) BCHTU 100 No cure 30 35 55 BOTU No cure No cure 50 50 50 *25silicone units ⁺50 silicone units ^(✓)10 silicone units - 10 ethyleneoxide (“EO”) units ^(x)15 silicone units - 15 EO units ^(@)25 siliconeunits - 10 EO units

What is claimed is:
 1. A process for preparing a reaction product from acurable composition, comprising the steps of: applying a compound withinstructures I or IA

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2, or

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2, to a desiredsubstrate surface, applying a composition comprising a (meth)acrylatecomponent and an oxidant to that desired substrate surface, mating asecond surface to that substrate surface to form an assembly, andexposing the assembly to appropriate conditions for a time sufficient tocure the composition.
 2. A process for preparing a reaction product froma curable composition, comprising the steps of: applying a compositioncomprising a (meth)acrylate component and an oxidant to a desiredsubstrate surface, applying a compound within structures I or IA

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2, or

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2, to that desiredsubstrate surface, mating a second surface to that substrate surface toform an assembly, and exposing the assembly to appropriate conditionsfor a time sufficient to cure the composition.
 3. A process forpreparing a reaction product from a curable composition, comprising thesteps of: applying an oxidant to a desired substrate surface, applying acomposition comprising a (meth)acrylate component and a compound withinstructures I or IA

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2, or

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2 to that desiredsubstrate surface, mating a second surface to that substrate surface toform an assembly, and exposing the assembly to appropriate conditionsfor a time sufficient to cure the composition.
 4. A process forpreparing a reaction product from a curable composition, comprising thesteps of: applying a composition comprising a (meth)acrylate componentand a compound within structures I or IA

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2, or

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2, to a desiredsubstrate surface, applying an oxidant to that desired substratesurface, mating a second surface to that substrate surface to form anassembly, and exposing the assembly to appropriate conditions for a timesufficient to cure the composition.
 5. A primer composition comprising acure accelerator within structures I or IA

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2, or

wherein R and R′ are independently selected from hydrogen, alkyl,alkenyl, aryl, hydroxyalkyl, hydroxyalkenyl, alkylene (meth)acrylate,carbonyl, carboxyl, or sulfonato, or R and R′ taken together form acarbocyclic or hetero atom-containing ring, or R′ is a direct bondattaching to the phenyl ring; X is halogen, alkyl, alkenyl, cycloalkyl,hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene- oralkenylene-ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso,sulfonate, hydroxyl or haloalkyl; and Y is —SO₂NH—, —CONH—, —NH—, and—PO(NHCONHCSNH₂)NH—; and n is 0 or 1 and m is 1 or 2.